BACKGROUND OF THE INVENTION
1. Field of the Invention
[0001] This invention relates generally to ceramic materials according to claim 1 and more
particularly to ceramic materials for insulators of spark plugs.
2. Description of the Prior Art
[0002] Spark plugs typically extend into the combustion chamber of an internal combustion
engine and include a cylindrical metal shell having a firing end and a hook shaped
ground electrode attached thereto. A cylindrical insulator is disposed partially within
the metal shell and extends axially beyond the metal shell toward the firing end and
also toward a terminal end. At the firing end, a cylindrical center electrode is disposed
within the insulator and projects axially out of the insulator toward the ground electrode,
wherein a spark gap is defined between the electrodes.
[0003] During operation, ignition voltage pulses are applied though the spark plug to the
center electrode, thereby causing a spark to jump the spark gap between the center
electrode and ground electrode. The spark ignites an air and fuel mixture within the
combustion chamber to create high temperature combustion to power the engine. The
ceramic insulator is used to isolate the high voltage at the electrodes, ensuring
that the spark happens at the tip of the center electrode and not anywhere else on
the spark plug. The insulator is subjected to harsh conditions at temperatures of
up to about 1000° C, and therefore, is typically formed of a ceramic material to provide
adequate thermal conductivity and dielectric strength.
[0004] However, as combustion engines become more complex, operating at high temperatures,
and requiring higher voltages for the spark to jump the spark gap, the performance
demands for ceramic insulators increase. In addition, manufacturers desire to increase
the service lifetimes of spark plug insulators while keeping the size and cost of
the spark plug insulator to a minimum.
[0005] One aspect of the invention provides a ceramic material for an insulator of a spark
plug comprising, in weight percent (wt%) of the ceramic material, aluminum oxide (Al
2O
3) in an amount of 98.00 wt% to 99.50 wt%; at least one oxide of a Group 2 alkaline
earth metal (Group 2 oxide) in an amount of 0.16 wt% to 0.70 wt%;
at least one oxide of a Group 4 transition metal (Group 4 oxide) in an amount of 0.01 wt%
to 0.16 wt%; and silicon dioxide (SiO
2) in an amount of 0.25 wt% to 0.75 wt%. The Group 2 oxides are selected from the group
consisting of calcium oxide (CaO), magnesium oxide (MgO), beryllium oxide (BeO), strontium
oxide (SrO), barium oxide (BaO), and radium oxide (RaO). The Group 4 oxides are selected
from the group consisting of: zirconium oxide (ZrO
2), titanium dioxide (TiO
2), hafnium oxide (HfO
2), and rutherfordium oxide (RfO
2). The Al
2O
3 powder used to prepare the ceramic has a D50 median particle size by volume of 1.2
µm to 1.8 µm and a D90 particle size by volume of 2.5 µm to 6.0 µm.
[0006] The wt% of a component of the ceramic material is defined as the concentration of
the component relative to the total amount of the ceramic material. The presence and
amount of the Al
2O
3, Group 2 oxides, Group 4 oxides, and SiO
2, are measured by x-ray fluorescence (XRF) or Inductively Coupled Plasma (ICP) after
sintering the ceramic material. A particle size distribution of the Al
2O
3 is measured using a Beckman-Coulter LS-230 laser scattering instrument before pressing
and sintering the ceramic material. The median particle size is determined from the
particle size distribution. The D50 median particle size by volume is the equivalent
spherical diameter of the particle where 50.0 % of the particles have a larger equivalent
diameter, and the other 50.0 % have a smaller equivalent diameter. The D50 median
particle size by volume is the equivalent spherical diameter of the particle where
50.0 % of the particles have a larger equivalent diameter, and the other 50.0 % have
a smaller equivalent diameter. The D90 particle size by volume is the equivalent spherical
diameter of the particle where 90.0 % of the particles have a particle size smaller
than the D90 equivalent diameter.
[0007] Another aspect of the invention provides an insulator formed of a ceramic material
for a spark plug comprising, in wt% of the ceramic material, Al
2O
3 in an amount of 98.00 wt% to 99.50 wt%; at least one Group 2 oxide in an amount of
0.16 wt% to 0.70 wt%; at least one Group 4 oxide in an amount of 0.01 wt% to 0.16
wt%; and SiO
2 in an amount of 0.25 wt% to 0.75 wt%. The Group 2 oxides are selected from the group
consisting of calcium oxide (CaO), magnesium oxide (MgO), beryllium oxide (BeO), strontium
oxide (SrO), barium oxide (BaO), and radium oxide (RaO). The Group 4 oxides are selected
from the group consisting of: zirconium oxide (ZrO
2), titanium dioxide (TiO
2), hafnium oxide (HfO
2), and rutherfordium oxide (RfO
2). The Al
2O
3 has a D50 median particle size by volume of 1.2µm to 1.8 µm_and a D90 particle size
by volume of 2.5 µm to 6.0 µm.
[0008] Another aspect of the invention provides a spark plug including an insulator formed
of a ceramic material comprising, in wt% of the ceramic material, Al
2O
3 in an amount of 98.00 wt% to 99.50 wt%; at least one Group 2 oxide in an amount of
0.16 wt% to 0.70 wt%; at least one Group 4 oxide in an amount of 0.01 wt% to 0.16
wt%; and SiO
2 in an amount of 0.25 wt% to 0.75 wt%. The Group 2 oxides are selected from the group
consisting of calcium oxide (CaO), magnesium oxide (MgO), beryllium oxide (BeO), strontium
oxide (SrO), barium oxide (BaO), and radium oxide (RaO). The Group 4 oxides are selected
from the group consisting of: zirconium oxide (ZrO
2), titanium dioxide (TiO
2), hafnium oxide (HfO
2), and rutherfordium oxide (RfO
2). The Al
2O
3 has a D50 median particle size by volume of 1.2_µm to 1.8 µm and a D90 particle size
by volume of 2.5 µm to 6.0 µm.
[0009] Yet another aspect of the invention provides a method of fabricating a ceramic material
for an insulator of a spark plug comprising the steps of providing ceramic particles
comprising, in wt% of the ceramic material, Al
2O
3 having a D50 median particle size by volume of 1.2 µm to 1.8 µm and a D90 particle
size by volume of 2.5 µm to 6.0 µm in amount of 98.00 wt% to 99.50 wt%, at least one
Group 2 oxide in an amount of 0.16 wt% to 0.70 wt%, wherein the Group 2 oxides are
selected from the group consisting of calcium oxide (CaO), magnesium oxide (MgO),
beryllium oxide (BeO), strontium oxide (SrO), barium oxide (BaO), and radium oxide
(RaO), at least one Group 4 oxide in an amount of 0.01 wt% to 0.16 wt%, wherein the
Group 4 oxides are selected from the group consisting of zirconium oxide (ZrO
2), titanium dioxide (TiO
2), hafnium oxide (HfO
2), and rutherfordium oxide (RfO
2), and SiO
2 in an amount of 0.25 wt% to 0.75 wt%; pressing the ceramic particles; and sintering
the ceramic particles.
[0010] Another aspect of the invention provides a method of fabricating an insulator formed
of a ceramic material for a spark plug comprising the steps of providing ceramic particles
comprising, in wt% of the ceramic material, Al
2O
3 having a D50 median particle size by volume of 1.2 µm to 1.8 µm and a D90 particle
size by volume of 2.5 µm to 6.0 µm in amount of 98.00 wt% to 99.50 wt%, at least one
Group 2 oxide in an amount of 0.16 wt% to 0.70 wt%, wherein the Group 2 oxides are
selected from the group consisting of calcium oxide (CaO), magnesium oxide (MgO),
beryllium oxide (BeO), strontium oxide (SrO), barium oxide (BaO), and radium oxide
(RaO), at least one Group 4 oxide in an amount of 0.01 wt% to 0.16 wt%, wherein the
Group 4 oxides are selected from the group consisting of zirconium oxide (ZrO
2), titanium dioxide (TiO
2), hafnium oxide (HfO
2), and rutherfordium oxide (RfO
2), and SiO
2 in an amount of 0.25 wt% to 0.75 wt%; pressing the ceramic particles; sintering the
ceramic particles; and forming the ceramic particles to a predetermined shape.
[0011] The ceramic material for the spark plug insulator provides an improved thermal conductivity
and dielectric strength compared to prior art ceramic insulators. Therefore, the ceramic
material provides longer service life and improved performance within the high temperature,
high voltage environment of the combustion chamber, without a significant increase
in size or cost of the ceramic insulator.
BRIEF DESCRIPTION OF THE DRAWINGS
[0012] Other advantages of the present invention will be readily appreciated, as the same
becomes better understood by reference to the following detailed description when
considered in connection with the accompanying drawings wherein:
Figure 1 is a partial fragmentary view of a spark plug having a ceramic insulator
in accordance with the subject invention;
Figure 2 (top) is a photomicrograph of one embodiment of the inventive ceramic material
(08-B-10) at 200x magnification;
Figure 2 (bottom) is a photomicrograph of one embodiment of the inventive ceramic
material (08-B-10) at 1000x magnification;
Figure 3 (top) is a photomicrograph of a prior art ceramic material (09-B-23) at 200x
magnification; and
Figure 3 (bottom) is a photomicrograph of a prior art ceramic material (09-B-23) at
500x magnification.
DETAILED DESCRIPTION OF THE INVENTION
[0013] Referring to Figure 1, a representative spark plug 20 for igniting a mixture of fuel
and air in an internal combustion engine is shown. The spark plug 20 includes an insulator
22 formed of a ceramic material comprising, in weight percent (wt%) of the ceramic
material, aluminum oxide (Al
2O
3) in an amount of 98.00 wt% to 99.50 wt%; at least one oxide of a Group 2 alkali earth
metal (Group 2 oxide) in an amount or 0.16 wt% to 0.70 wt%; and silicon dioxide (SiO
2) in an amount of 0.25 wt% to 0.75 wt%. The Al
2O
3 has a median particle size (D50) by volume of 1.2 microns (µm) to 1.8 µm. The ceramic
material is fabricated by providing ceramic particles including Al
2O
3, at least one Group 2 oxide, and SiO
2; pressing the ceramic particles; and sintering the ceramic particles.
[0014] The wt% of a component of the ceramic material is defined as the concentration of
the component relative to the total amount of the ceramic material. For example, if
the ceramic material includes Al
2O
3 in an amount of 99.00 wt%, then 99.00% of the total ceramic material consists of
Al
2O
3, and the remaining 1.00% of the total ceramic material consists of other compounds.
The presence and amount of the Al
2O
3, Group 2 oxides, and SiO
2 of the ceramic material are measured by x-ray fluorescence (XRF) or Inductively Coupled
Plasma (ICP) after sintering the ceramic material. A particle size distribution of
the Al
2O
3 is measured using a Beckman-Coulter LS-230 laser scattering instrument before pressing
and sintering the ceramic material. The median particle size is determined from the
particle size distribution.
[0015] The representative spark plug 20 assembly includes a metal shell 24, an insulator
22, a center electrode 26, and a ground electrode 28, as shown in Figure 1. As commonly
known in the art, the metal shell 24 is a generally cylindrical, electrically conductive
component having a hollow bore extending along its axial length. Within that bore
are a series of circumferential shoulders sized to support diametrically reduced sections
of the insulator
22. Like the metal shell
24, the insulator
22 also has a generally cylindrical shape and includes an elongated axial bore. The
lower axial end of the insulator
22 comprises a nose portion which generally extends out of and beyond the lowermost
portion of the metal shell
24 and toward a firing end
36. The axial bore of the insulator
22 is designed to receive a terminal electrode
30 at one end and the center electrode
26 at the firing end
36. A center wire assembly
32 extends from the terminal electrode
30 to the center electrode
26. The ground electrode
28 is both mechanically and electrically connected to the lower axial end of the metal
shell
24. The exposed end of the center electrode
26 and a side surface of the ground electrode
28 oppose each other and thereby define a spark gap
34 at the firing end
36 of the spark plug
20. The spark plug
20 shown in Figure 1 and described herein is only one example embodiment among many
possible embodiments.
[0016] In operation, the terminal electrode
30 receives a high voltage ignition pulse from an ignition system (not shown) which
travels along the center wire assembly
32 until it reaches the lower exposed end of the center electrode
26. If the pulse has sufficient energy to bridge the spark gap
34, a spark is formed between the center electrode
26 and the ground electrode
28, which in turn is grounded to the engine via the metal shell
24. The spark ignites a fuel/air mixture which has previously been injected into a combustion
chamber within the engine, which in turn initiates the combustion process used to
power the engine.
[0017] The insulator
22 of the spark plug
20 is formed of a ceramic material comprising Al
2O
3 in an amount sufficient to affect the thermal conductivity and dielectric strength
of the ceramic material. The ceramic material includes, in wt% of the ceramic material,
the Al
2O
3 in an amount of 98.00 wt% to 99.50 wt%. In another embodiment, the ceramic material
includes the Al
2O
3 in an amount of 98.50 wt% to 99.30 wt%. In yet another embodiment, the ceramic material
includes the Al
2O
3 in an amount of 98.90 wt% to 99.10 wt%. As stated above, the presence and amount
of Al
2O
3 is measured by x-ray fluorescence (XRF) or Inductively Coupled Plasma (ICP) after
sintering the ceramic material.
[0018] The Al
2O
3 is provided in the form of ceramic particles having a particle size sufficient to
affect the porosity, density, and dielectric strength of the ceramic material. In
one embodiment, the Al
2O
3 has a D50 median particle size by volume of 1.2 µm to 1.8 µm. In another embodiment,
the Al
2O
3 has a D50 median particle size by volume of 1.3 µm to 1.7 µm. In yet another embodiment,
the Al
2O
3 has a D50 median particle size by volume of 1.4 µm to 1.6 µm. The D50 median particle
size is the equivalent spherical diameter of the particle where 50.0 % of the particles
have a larger equivalent diameter, and the other 50.0 % have a smaller equivalent
diameter. As stated above, the particle size distribution is measured using a Beckman-Coulter
LS-230 laser scattering instrument before pressing and sintering the ceramic particles,
and the median particle size is determined from the particle size distribution.
[0019] The particle size distribution can also be described as a D90 particle size. In one
embodiment, the Al
2O
3 has a D90 particle size by volume of 2.5 µm to 6.0 µm. In another embodiment, the
Al
2O
3 has a D90 particle size by volume of 2.9 µm to 5.1 µm. In yet another embodiment,
the Al
2O
3 has a D90 particle size by volume of 3.5 µm to 4.5 µm. The D90 particle size by volume
is the equivalent spherical diameter of the particle where 90.0 % of the particles
have a particle size smaller than the D90 equivalent diameter. This particle size
distribution measurement is also conducted using a Beckman-Coulter LS-230 laser scattering
instrument before pressing and sintering the ceramic particles, and the D90 particle
size is determined from the particle size distribution.
[0020] The ceramic Al
2O
3 particles have a specific surface area sufficient to affect the porosity, density,
and dielectric strength of the ceramic material. In one embodiment, the Al
2O
3 has a specific surface area of 2.0 m
2/g to 5.0 m
2/g. In another embodiment, the Al
2O
3 has a specific surface area of 2.5 m
2/g to 4.5 m
2/g. In yet another embodiment, the Al
2O
3 has a specific surface area of 3.0 m
2/g to 4.0 m
2/g. The specific surface area of the Al
2O
3 particles is measured by the BET method using a Micromeritics Instrument Corporation
Gemini II Model 2370. The BET method involves determining the specific surface area
by measuring the amount of nitrogen gas that is absorbed on the surface of the ceramic
particles in order to form a single layer of molecules. The specific surface area
of the Al
2O
3 is measured before pressing and sintering the ceramic particles.
[0021] The ceramic insulator includes at least one Group 2 oxide in an amount sufficient
to affect the thermal conductivity and dielectric strength of the ceramic material.
The ceramic material includes, in wt% of the ceramic material, the at least one Group
2 oxide in an amount of 0.16 wt% to 0.70 wt%. In one embodiment, the ceramic material
includes the at least one Group 2 oxide in an amount of 0.33 wt% to 0.60 wt%. In yet
another embodiment, the ceramic material includes the at least one Group 2 oxide in
an amount of 0.40 wt% to 0.53 wt%. The wt% of the at least one Group 2 oxide is equal
to the sum of the wt% of each Group 2 oxide of the ceramic material relative to the
total amount of the ceramic material. In other words, the wt% of the at least one
Group 2 oxide is defined as the concentration of the Group 2 oxides relative to the
total amount of the ceramic material. The presence and amount of the Group 2 oxides
are measured by x-ray fluorescence (XRF) or Inductively Coupled Plasma (ICP) after
sintering the ceramic material.
[0022] The Group 2 oxides of the ceramic material include at least one of the group comprising
calcium oxide (CaO), magnesium oxide (MgO), beryllium oxide (BeO), strontium oxide
(SrO), barium oxide (BaO), and radium oxide (RaO). In one embodiment, the Group 2
oxides of the ceramic material include calcium oxide (CaO) and magnesium oxide (MgO)
in an amount of 0.16 wt% to 0.70 wt%.
[0023] In one embodiment, the ceramic material includes, in wt% of the ceramic material,
the CaO in an amount of 0.1 wt% to 0.55 wt%. In another embodiment, the ceramic material
includes the CaO in an amount of 0.30 wt% to 0.50 wt%. In yet another embodiment,
the ceramic material includes the CaO in an amount of 0.35 wt% to 0.45 wt%. The presence
and amount of CaO is measured by x-ray fluorescence (XRF) or Inductively Coupled Plasma
(ICP) after sintering the ceramic material.
[0024] In one embodiment, the ceramic material includes, in wt% of the ceramic material,
the MgO in an amount of 0.01 wt% to 0.15 wt %. In another embodiment, the ceramic
material includes the MgO in an amount of 0.03 wt% to 0.10 wt%. In yet another embodiment,
the ceramic material includes the MgO in an amount of 0.05 wt% to 0.08 wt%. The presence
and amount of MgO is measured by x-ray fluorescence (XRF) or Inductively Coupled Plasma
(ICP) after sintering the ceramic material.
[0025] The ceramic material includes silicon dioxide (SiO
2) in an amount sufficient to affect the thermal conductivity and dielectric strength
of the ceramic material. The ceramic material includes, in wt% of the ceramic material,
the SiO
2 in an amount of 0.25 wt% to 0.75 wt%. In one embodiment, the ceramic material includes
the SiO
2 in an amount of 0.50 wt% to 0.70 wt%. In yet another embodiment, the ceramic material
includes the SiO
2 in an amount of 0.55 wt% to 0.65 wt%. The presence and amount of SiO
2 is measured by x-ray fluorescence (XRF) or Inductively Coupled Plasma (ICP) after
sintering the ceramic material.
[0026] In one embodiment, the ceramic material includes at least one oxide of a Group 4
transition metal (Group 4 oxide) in an amount sufficient to affect the thermal conductivity
and dielectric strength of the ceramic material. In one embodiment, the ceramic material
includes, in wt% of the ceramic material, the at least one Group 4 oxide in amount
of 0.01 wt% to 0.16 wt%. In another embodiment, the ceramic material includes the
at least one Group 4 oxide in amount of 0.04 wt% to 0.13 wt%. In yet another embodiment,
the ceramic material includes the at least one Group 4 oxide in amount of 0.07 wt%
to 0.10 wt%. The presence and amount of the Group 4 oxides are measured by x-ray fluorescence
(XRF) or Inductively Coupled Plasma (ICP) after sintering the ceramic material.
[0027] The Group 4 oxides of the ceramic material include at least one of zirconium oxide
(ZrO
2), titanium dioxide (TiO
2), hafnium oxide (HfO
2), and rutherfordium oxide (RfO
2). In one embodiment, the Group 4 oxides include ZrO
2 and TiO
2 in an amount of 0.07 wt% to 0.10 wt%.
[0028] In one embodiment, the ceramic material includes, in wt% of the ceramic material,
the ZrO
2 in an amount of 0.01 wt% to 0.15 wt%. In another embodiment, the ceramic material
includes the ZrO
2 in an amount of 0.04 wt% to 0.12 wt%. In yet another embodiment, the ceramic material
includes the ZrO
2 in an amount of 0.07 wt% to 0.09 wt%. The presence and amount of ZrO
2 is measured by x-ray fluorescence (XRF) or Inductively Coupled Plasma (ICP) after
sintering the ceramic material.
[0029] In one embodiment, the ceramic material includes, in wt% of the ceramic material,
the TiO
2 in an amount of up to 0.01 wt%. In another embodiment, the ceramic material includes
the TiO
2 in an amount of up to 0.006 wt %. In yet another embodiment, the ceramic material
includes the TiO
2 in an amount of up to 0.004 wt %. The presence and amount of TiO
2 is measured by x-ray fluorescence (XRF) or Inductively Coupled Plasma (ICP) after
sintering the ceramic material.
[0030] In one embodiment, the ceramic material includes at least one oxide of a Group 1
alkali metal (Group 1 oxide) in an amount sufficient to affect the thermal conductivity
and dielectric strength of the ceramic material. In one embodiment, the ceramic material
includes, in wt% of the ceramic material, the at least one Group 1 oxide in an amount
of less than 0.0060 wt%. In another embodiment, the ceramic material includes the
at least one Group 1 oxide in an amount of less than 0.0040 wt%. In yet another embodiment,
the ceramic material includes the at least one Group 1 oxide in an amount of less
than 0.0020 wt%. The presence and amount of the Group 1 oxides are measured by x-ray
fluorescence (XRF) or Inductively Coupled Plasma (ICP) after sintering the ceramic
material.
[0031] The Group 1 oxides of the ceramic material include at least one of potassium oxide
(K
2O), sodium oxide (Na
2O), lithium oxide (Li
2O), rubidium oxide (Rb
2O), cesium oxide (Cs
2O), and francium oxide (Fr
2O). In one embodiment, the Group 1 oxides of the ceramic material include K
2O and Na
2O in an amount of less than 0.0060 wt%.
[0032] In one embodiment, the ceramic material includes at least one Group 2 oxide, at least
one Group 4 oxide, and at least one Group 1 oxide. In another embodiment, the ceramic
material includes at least one Group 2 oxide and at least one Group 4 oxide. In yet
another embodiment, the ceramic material includes at least one Group 2 oxide and at
least one Group 1 oxide.
[0033] In one embodiment, the ceramic material includes, in wt% of the ceramic material,
the K
2O in an amount of less than 0.0050 wt%. In another embodiment, the ceramic material
includes the K
2O in an amount of less than 0.0030 wt%. In yet another embodiment, the ceramic material
includes the K
2O in an amount of less than 0.0020 wt%. The presence and amount of K
2O is measured by x-ray fluorescence (XRF) or Inductively Coupled Plasma (ICP) after
sintering the ceramic material.
[0034] In one embodiment, the ceramic material includes, in wt% of the ceramic material,
the Na
2O in an amount of up to 0.0010 wt%. In another embodiment, the ceramic material includes
the Na
2O in an amount up to 0.0009 wt%. In yet another embodiment, the ceramic material includes
the Na
2O in an amount up to 0.0007 wt%. The presence and amount of Na
2O is measured by x-ray fluorescence (XRF) or Inductively Coupled Plasma (ICP) after
sintering the ceramic material.
[0035] In one embodiment, the ceramic material includes phosphorous pentoxide (P
2O
5) in an amount sufficient to affect the thermal conductivity and dielectric strength
of the ceramic material. In one embodiment, the ceramic material includes, in wt%
of the ceramic material, the P
2O
5 in an amount of less than 0.0040 wt%. In another embodiment, the ceramic material
includes the P
2O
5 in an amount of 0.0010 wt% to 0.0035 wt %. In yet another embodiment, the ceramic
material includes the P
2O
5 in an amount of 0.0025 wt% to 0.0030 wt %. The presence and amount of the P
2O
5 is measured by x-ray fluorescence (XRF) or Inductively Coupled Plasma (ICP) after
sintering the ceramic material.
[0036] In one embodiment, the ceramic material includes boron oxide (B
2O
3) in an amount sufficient to affect the thermal conductivity and dielectric strength
of the ceramic material. In one embodiment, the ceramic material includes, in wt%
of the ceramic material, the B
2O
3 in an amount up to 0.50 wt%. In another embodiment, the ceramic material includes
the B
2O
3 in an amount up to 0.40 wt%. In yet another embodiment, the ceramic material includes
the B
2O
3 in an amount up to 0.30 wt%. The presence and amount of the B
2O
3 is measured by Inductively Coupled Plasma (ICP) after sintering the ceramic material.
[0037] In one embodiment, the ceramic material is combined with a binder in an amount sufficient
to adhere the components of the ceramic material to one another. The binder is not
included in the composition of the ceramic material when determining wt% of each component.
The binder preferably includes an organic resin or wax, such as polyvinyl alcohol
(PVA), polyethylene glycol (PEG), wax, or an emulsion including wax, water, and emulsifying
agents, or a mixture of these organic resins and waxes. The binder is added in an
amount of about 1.5 wt% to about 2.5 wt%, based on the dry weight of the ceramic powder.
Typically, the binder burns off cleanly during the sintering step and is not present
in the sintered ceramic material.
[0038] In one embodiment, at least a portion of the Al
2O
3, Group 2 oxides, and SiO
2 combine during sintering to form a glass phase. The sintered ceramic material includes,
in wt% of the ceramic material, the glass phase in an amount of 0.50 wt% to 2.0 wt%.
In another embodiment, the sintered ceramic includes the glass phase in an amount
of 0.75 wt% to 1.5 wt%. In yet another embodiment, the sintered ceramic includes the
glass phase in an amount of 0.85 wt% to 1.15 wt%. Comparable prior art ceramic materials
typically include a glass phase in an amount of 4.0 wt% to 5.0 wt%. The presence of
the glass phase in the sintered ceramic material is measured using x-ray diffraction
(XRD) or by electron diffraction using an analytical screening transmission electron
microscope (ASTEM) after sintering the ceramic material. The amount of glass phase
can be estimated using x-ray fluorescence (XRF) or Inductively Coupled Plasma (ICP)
after sintering the ceramic material.
[0039] In one embodiment, the glass phase includes, in wt% of the glass phase, the Al
2O
3 in an amount of 5.0 wt% to 50.0 wt%. In another embodiment, the glass phase includes
the Al
2O
3 in an amount of 15.0 wt% to 45.0 wt%. In yet another embodiment, the glass phase
includes the Al
2O
3 in an amount of 31.0 wt% to 39.0 wt%. The presence of the Al
2O
3 in the glass phase is measured using energy dispersive spectroscopy EDS or EDX using
a analytical scanning transmission electron microscope (ASTEM) after sintering the
ceramic material. The amount of Al
2O
3 in the glass phase is difficult to determined analytically, but an Al
2O
3-SiO
2-MgO-CaO phase diagram indicates the Al
2O
3 is typically present in an amount of 15.0 wt% to 45.0 wt%.
[0040] In one embodiment, the glass phase includes, in wt% of the glass phase, the Group
2 oxides in an amount of 15.5 wt% to 31.7 wt%. In another embodiment, the glass phase
includes the Group 2 oxides in an amount of 17.0 wt% to 27.5 wt%. In yet another embodiment,
the glass phase includes the Group 2 oxides in an amount of 21.2 wt% to 25.0 wt%.
The presence of the Group 2 oxides in the glass phase is measured using energy dispersive
spectroscopy EDS or EDX using a analytical scanning transmission electron microscope
(ASTEM) after sintering the ceramic material.
[0041] In one embodiment, the Group 2 oxides of the glass phase include CaO in an amount
of 15.0 wt% to 24.0 wt% and MgO in an amount of 0.5 wt% to 7.7 wt%. In another embodiment,
the Group 2 oxides include CaO in an amount of 17.0 wt% to 22.4 wt% and MgO in an
amount of 0.9 wt% to 5.5 wt%. In another embodiment, the Group 2 oxides include CaO
in an amount 19.0 wt% to 20.0 wt% and MgO in an amount of 2.5 wt% to 4.6 wt%.
[0042] In one embodiment, the glass phase includes, in wt% of the glass phase, the SiO
2 in an amount of 27.0 wt% to 50.0 wt%. In another embodiment, the glass phase includes
the SiO
2 in an amount of 34.0 wt% to 47.3 wt%. In yet another embodiment, the glass phase
includes the SiO
2 in an amount of 40.0 wt% to 43.2 wt%. The presence of the SiO
2 in the glass phase using energy dispersive spectroscopy EDS or EDX using a analytical
scanning transmission electron microscope (ASTEM) after sintering the ceramic material.
[0043] In one embodiment, at least a portion of the Al
2O
3, Group 2 oxides, and SiO
2 combine during sintering to form secondary crystals. The secondary crystals include
at least one of calcium hexa-aluminate (CaAl
12O
19) spinel (MgAl
2O
4), anorthite (CaAl
2Si
2O
8), and mullite (Al
6Si
2O
13). The presence and amount of the secondary crystals are measured by a Scanning Electron
Microscope (SEM) with energy-dispersive X-ray spectroscopy (EDS). The phase composition
of the secondary crystals is measured using X-ray diffraction (XRD) or by electron
diffraction using an analytical scanning transmission electron microscope (ASTEM).
The sintered ceramic material typically includes the secondary crystals in an amount
of less than 1.0%. The presence of the Al
2O
3, Group 2 oxides, and SiO
2 in each of the secondary crystals is also measured by a Scanning Electron Microscope
(SEM) with energy-dispersive X-ray spectroscopy (EDS). The amount of the Al, O, Si
and Group 2 elements in the secondary crystals is difficult to determine analytically
due to the low amount of secondary crystals in the sintered ceramic material.
[0044] Table 1 includes Inventive Example 1 which is one of the many embodiments of the
inventive ceramic material. Table 1 also includes Comparative Example 1, which is
a prior art ceramic material.
Table 1
| |
Al2O3 |
Group 2 Oxides |
SiO2 |
| |
wt% |
wt% |
wt% |
| Inventive Example 1 |
98.85 |
0.46 |
0.60 |
| |
|
|
|
| Comparative Example 1 |
95.38 |
1.89 |
2.43 |
[0045] Table 2 includes Inventive Examples 2 and 3, which are two more particular embodiments
of the many embodiments of the inventive ceramic material. Figure 2 (top) a photomicrograph
of Inventive Example 1 (08-B-10) at 200x magnification. Figure 2 (bottom) is a photomicrograph
of Inventive Example 1 (08-B-10) at 1000x magnification. Table 2 also includes Comparative
Example 2, which is another prior art ceramic material. Figure 3 (top) is a photomicrograph
of the prior art, Comparative Example 2 (09-B-23) at 200x magnification. Figure 3
(bottom) is a photomicrograph of the prior art, Comparative Example 2 (09-B-23) at
500x magnification. After sintering, the ceramic material of Inventive Example 2 includes
a glass phase in an amount of about 1.0 wt% and the ceramic material of Comparative
Example 2 includes a glass phase in an amount of about 4.0 wt%.
Table 2
| |
|
Group 2 Oxides wt% |
|
Group 4 Oxides wt% |
Group 1 Oxides wt% |
|
| Al2O3 wt% |
CaO wt% |
MgO wt% |
SiO2 wt% |
TiO2 wt% |
ZrO2 wt% |
K2O wt% |
Na2O wt% |
P2O5 wt% |
| Inventive Example 2 |
98.85 |
0.39 |
0.073 |
0.60 |
0.004 |
0.08 |
0.003 |
0.0007 |
0.0027 |
| (ID.No. 08-B-10) |
|
|
|
|
|
|
|
|
|
| Inventive Example 3 |
98.80 |
0.46 |
0.037 |
0.62 |
0.005 |
0.08 |
0.004 |
0.0008 |
0.0031 |
| (ID Nos. 09-B-41) |
|
|
|
|
|
|
|
|
|
| Comparative Example 2 |
95.38 |
1.55 |
0.29 |
2.43 |
0.015 |
0.30 |
0.014 |
0.0027 |
0.0105 |
| (ID No. 09-B-23) |
|
|
|
|
|
|
|
|
|
[0046] Inventive Example 2 (08-B-10) may include the following commercially available products,
in wt % of the ceramic material, Almatis A152-SG Alumina in an amount of 98.19 wt%;
Edgar Plastic Kaolin (EPK) in an amount of 0.84 wt%; Yellowstone Talc in an amount
of 0.22 wt%; Hubercarb CaCO
3 in an amount of 0.68 wt%; and CC10 Zirconia in an amount of 0.08 wt%.
[0047] Further, the present invention includes the method of fabricating the ceramic material
for an insulator
22 of a spark plug
20. As alluded to above, the method includes providing the Al
2O
3 in the form of ceramic particles having a median particle size of 1.2 µm to 1.8 µm.
In one embodiment, the method includes providing the other components of the ceramic
material, including the CaO, MgO, SiO
2, TiO
2ZrO
2, K
2O, Na
2O, and P
2O
5. in the form of ceramic particles. As alluded to above, the method includes providing
the Al
2O
3 in an amount of 98.00 wt% to 99.50 wt%, and providing the at least one Group 2 oxide
in an amount of 0.16 wt% to 0.70 wt%; and providing the SiO
2 in an amount of 0.25 wt% to 0.75 wt%.
[0048] One embodiment of the method includes milling a suspension of the ceramic particles
dispersed in water for about six hours. The embodiment includes adding a deflocculating
agent such as Darvan 821 A and a binder to the suspension. The embodiment next includes
spray drying the ceramic particles using a spray drier, such as a Bowen #1 spray dryer
operating at an outlet temperature of about 125° C. Next, the embodiment includes
screening the spray dried ceramic particles to a size of about -60 mesh. The embodiment
includes forming the ceramic particles to a predetermined shape, for example pressing
the ceramic particles to a pressure of about 30,000 psi and the predetermined shape.
However, the ceramic particles may be pressed to other pressures. As alluded to above,
in one embodiment, the ceramic particles are pressed to a generally cylindrical shape
to form the insulator
22 shown in Figure 1. In one embodiment, the outer surface of the insulator
22 is shaped the a final shape using a grinding wheel. Next, the embodiment includes
sintering or firing the pressed ceramic material to a temperature of about 1600° C
with about a dwell time of about three hours.
[0049] The sintered ceramic material of the present invention provides improved properties
and performance for use as a spark plug insulator
22, compared to prior art ceramic insulators. The sintered ceramic material of the present
invention includes a plurality of pores, also referred to as void spaces. Each pore
of the ceramic material has a maximum pore size of less than 15.0 µm and median pore
size of about 3.0 µm. The pore size is measured by the equivalent spherical diameter
(ESD) of a single pore. The sintered ceramic material has a porosity, in area percent
(area %) of the ceramic material, up to 1.50 area %. The total area of the ceramic
material includes both the area of the solid components and area of the pores. The
porosity is equal to the sum of the areas of each pore of the ceramic material. In
other words, the porosity is obtained by determining the area of each pore of the
ceramic material, and then adding the areas. The pore sizes and porosity are determined
after sintering the ceramic material.
[0050] The porosity and pore sizes of the ceramic material are determined using a reflected
light microscope, such as a Nikon ME600 DP with differential interference contrast
(DIC) to view a sample of the ceramic material. The microscope includes a ruler or
another measuring tool to measure the EDS and area of each visible pore. Figure 2
(top) shows the microstructure and pores of Inventive Example 1 (08-B-10) at 200x
magnification. Figure 2 (bottom) shows the microstructure and pores of the of the
Inventive Example 1 (08-B-10) at 1000x. Figure 2 also identifies pores and grains
and their corresponding sizes. Figure 3 (top) shows the microstructure and pores of
the prior art ceramic material, Comparative Example 2 (09-B-23) at 200x magnification.
Figure 3 (bottom) shows the microstructure and pores of the Comparative Example 2
(09-B-23) at 500x. Figure 3 also identifies pores and grains and their corresponding
size.
[0051] Testing was conducted to compare the median pore size, maximum pore size, total pore
area, and porosity of one embodiment of the inventive ceramic material (08-B-10) to
the prior art ceramic material (09-B-23). Specimens of each material were processed
by conventional milling, spray drying, pressing into disks at 10,000 psi, and firing
at about 1580° C in a lab kiln. The sintered specimens were prepared for analysis
by cutting a centerline section of each specimen with a diamond wafering saw. The
resulting section was mounted using a quick-setting epoxy resin. The mounted samples
were polished using an automatic polishing system. Final polishing and mechanical
etching was accomplished using a high pH aqueous 0.06 µm colloidal silica slurry.
Four images per specimen were obtained at the 200x magnification and analyzed using
ImagePro Ver. 5 image analysis and processing software. Table 3 reports the median
pore size, maximum pore size, total pore area, and porosity (area %), of the two specimens.
The total pore area, in microns squared (µm
2), includes the sum of the pore areas of the four specimens. The pore sizes and porosity
are the average of the four specimens. Table 4 reports, in µm, the size measured in
ESD of the ten largest pores observed in all four images for each specimen. As shown
in Tables 3 and 4, the Inventive Example 1 (08-B-10) has a lower pore size, total
pore area, and porosity than the prior art, Comparative Example 2 (09-B-23).
Table 3 - Pore Size, Pore Area, and Porosity Data
| |
Median Pore Size (ESD, µm) |
Max. Pore Size (ESD, µm) |
Total Pore Area (4 images, µm2) |
Porosity (Area %) |
| Inventive Example 2 |
3.1 |
14.7 |
17,358 |
1.70 |
| (ID No. 08-8-10) |
|
|
|
|
| |
|
|
|
|
| Comparative Example 2 |
4.8 |
25.8 |
44,692 |
4.38 |
| (ID Nos. 09-B-23) |
|
|
|
|
Table 4 - Ten Largest Pores Data (ESD, µm)
| ID |
1 |
2 |
3 |
4 |
5 |
6 |
7 |
8 |
9 |
10 |
| Inventive Example 2 |
14.7 |
13.4 |
12.2 |
11.9 |
11.7 |
11.6 |
11.5 |
11.4 |
11.3 |
11.2 |
| (ID No. 08-B-10) |
|
|
|
|
|
|
|
|
|
|
| |
|
|
|
|
|
|
|
|
|
|
| Comparative Example 2 |
25.8 |
24.4 |
23.2 |
21.4 |
21.1 |
20.0 |
19.9 |
19.6 |
19.1 |
18.6 |
| (ID Nos. 09-B-23) |
|
|
|
|
|
|
|
|
|
|
[0052] Testing was also conducted to measure the median pore size, maximum pore size, porosity,
and average grain size of one embodiment of the inventive ceramic material (09-B-29)
over a range of firing temperatures. Specimens were processed by conventional milling,
spray drying, pressing into disks at 10,000 psi, and firing at a series of temperatures
from 1500° C to 1650° C in a lab kiln. The sintered specimens were prepared for analysis
by cutting a centerline section of each specimen with a diamond wafering saw. The
resulting sections were mounted using a quick-setting epoxy resin. The mounted samples
were polished using an automatic polishing system. Samples were initially ground using
bonded diamond discs and polished using 9 µm and 3 µm diamond slurries. Final polishing
and mechanical etching was accomplished using a aqueous 0.05 µm colloidal alumina
slurry. Pore size observations were made using a reflected light microscope at magnifications
up to 1000x and images were captured using an attached camera system. Four images
per specimen were obtained at the 200x magnification and analyzed using ImagePro Ver.
5 image analysis and processing software. Grain size analysis was performed on thermally
etched sections of the specimens using SEM as per ASTM E-112-96. Table 5 reports the
median pore size and porosity of the specimens over a range of firing temperatures
from 1500° C to 1650° C. Table 6 reports average grain size of the specimens over
a range of temperatures from 1520° C to 1650° C.
Table 5 - Pore Size and Porosity Data
| Specimen Firing Temperature (° C) |
Median Pore Size (ESD, µm) |
Max. Pore Size (ESD, µm) |
Porosity (Area %) |
| 1500 |
3.1 |
27.8 |
4.7 |
| 1520 |
2.9 |
20.6 |
3.0 |
| 1550 |
3.0 |
18.3 |
2.0 |
| 1570 |
3.2 |
18.6 |
2.3 |
| 1580 |
3.1 |
18.9 |
5.1 |
| 1590 |
3.3 |
22.9 |
2.1 |
| 1600 |
3.3 |
18.3 |
2.0 |
| 1610 |
3.6 |
17.6 |
2.5 |
| 1620 |
3.5 |
26.4 |
2.3 |
| 1650 |
4.2 |
30.0 |
5.0 |
Table 6 - Mean Grain Size
| Specimen Firing Temperature (° C) |
Mean Grain Size (µm) |
| 1520 |
1.4 |
| 1550 |
1.7 |
| 1580 |
2.5 |
| 1600 |
2.7 |
| 1650 |
6.0 |
[0053] The inventive ceramic material has a higher green density, green strength, fired
bulk density, and fired relative density than prior art ceramic materials. Green density
is equal to the bulk density of the ceramic material after pressing and before sintering.
The bulk density is equal to the mass of the ceramic particles of the ceramic material
divided by the total volume of the ceramic material. As stated above, the total volume
of the ceramic material includes both the volume of the solid components and the volume
of the pores. Accordingly, the green density is measured after pressing and before
sintering. Green strength is the mechanical strength required to withstand mechanical
operations to which the ceramic material is subjected after pressing and before sintering,
without damaging its fine details and sharp edges. Accordingly, green strength is
measured after pressing but before sintering the ceramic material. The fired bulk
density and fired relative density are measured after sintering the ceramic material.
The fired bulk density is equal to the mass of the sintered ceramic material divided
by the total volume of the sintered ceramic material. The fired relative density is
the ratio of the fired bulk density of the ceramic material to the theoretical density
of the material..
[0054] Testing was conducted to compare the green density, green strength, fired bulk density,
and fired relative density of one embodiment of the inventive ceramic material (08-B-10)
to a prior art ceramic material (09-B-23). Specimens of each material were processed
by conventional milling, spray drying, pressing into disks at 9,500 psi, and firing
at about 1560° C, 1580° C, and 1600° C. The green density was tested after pressing
and before sintering. Table 7 reports the green density, green strength, fired bulk
density, and fired relative density of the specimens. As shown in Table 7, the inventive
ceramic material (08-B-10) has a higher green density, green strength, fired bulk
density, and fired relative density than the prior art ceramic material (09-B-23).
Table 7 - Green Density, Green Strength, Fired Bulk Density and Fired Relative Density
Data
| |
Green Density |
Green Strength |
Fired Bulk Density (g/cm3) |
Fired Relative Density (g/cm3) |
| 1560° C |
1580° C |
1600° C |
1560° C |
1580° C |
1600°C |
| Inventive Example 2 |
2.336 |
46.8 |
3.884 |
3.882 |
3.860 |
0.979 |
0.978 |
0.973 |
| (ID No.08-B-10) |
|
|
|
|
|
|
|
|
| |
|
|
|
|
|
|
|
|
| Comparative Example 2 |
2.302 |
44.4 |
3.766 |
3.766 |
3.756 |
0.958 |
0.958 |
0.955 |
| (ID Nos. 09-B-23) |
|
|
|
|
|
|
|
|
[0055] The inventive ceramic material has a greater dielectric breakdown strength (DBS)
than prior art ceramic materials. Dielectric breakdown strength is the maximum electric
field strength the ceramic material can withstand without breaking down, i.e. without
experiencing failure of its insulating properties.
[0056] Testing was conducted to compare the DBS of an inventive ceramic material (REG-G)
to a prior art ceramic material (REG-F). The inventive ceramic material (REG-G) has
the same composition as Inventive Example 2 (08-B-10) of Table 2 above. The prior
art ceramic material (REG-F) has the same composition as Comparative Example 2 (09-B-23)
of Table 2 above. Eleven insulator specimens were formed of the inventive ceramic
material (REG-G) and twelve insulator specimens were formed of the prior art ceramic
material (REG-F) by conventional milling, spray drying, pressing into cylindrical
blanks at 9,500 psi, cutting the desired profile into the unfired blanks using a grinding
wheel, and firing the blanks at about 1600° C. Each of the insulator specimens were
placed in a sample spark plug having a 10.0 millimeter thread design. The spark plugs
were tested by threading them into a test fixture and pressurized around the firing
end to prevent a spark from forming between the center electrode and ground electrode,
thus forcing dielectric puncture through the ceramic insulator specimens. A voltage
provided by an automotive ignition source was applied to the spark plugs and increased
in steps at a rate of 1 kV per second until failure occurred. After testing, the metallic
shells of the sample spark plugs were removed to verify that dielectric puncture had
occurred in the insulator specimens.
[0057] The dielectric testing results are shown in Table 8, indicating the inventive ceramic
material has an improved dielectric strength and performance, compared to the prior
art ceramic material. The inventive ceramic material (REG-G) had an average voltage
at failure of 46.4 kV, which was about 5.7% higher than the prior art ceramic material
(REG-F), which had average voltage at failure of 43.9 kV. More importantly, the minimum
voltage at failure of the sample spark plugs including the inventive ceramic material
(REG-G) was 41.0 kV, which was 5.1% higher than the minimum failure voltage of the
sample spark plugs including the prior art ceramic material (REG-F), which was 39.0
kV.
Table 8 - Dielectric Strength
| |
No. of Samples |
Average Voltage at Failure (kV) |
Minimum Voltage at Failure (kV) |
| Inventive Example 4 |
11 |
46.4 |
41.0 |
| (ID No. REG-G) |
|
|
|
| |
|
|
|
| Comparative Example 3 |
12 |
43.9 |
39.0 |
| (ID Nos. REG-F) |
|
|
|
[0058] The test results also indicate the lower pore size, lower pore area, and higher densities
reduce the weak spots of the ceramic material and the amount of trapped gas that can
become ionized in the ceramic material. Thus, the inventive ceramic material has a
higher DBS and a reduced likelihood of dielectric failure compared to prior art ceramic
materials.
[0059] Testing was also conducted to determined the correlation of pore size and pore area
with dielectric breakdown strength and correlation of one embodiment of the inventive
material (09-B-29) over a range of firing temperatures. As stated above, the dielectric
breakdown strength is the maximum electric field strength the ceramic material can
withstand intrinsically without breaking down. The specimens used for this testing
were disks with thickness of about 3.5 mm, while the dielectric testing previously
described was performed on insulators with wall thickness of 2.0 mm. The dielectric
breakdown strength was measured according to ASTM D-149. Pore size and pore area were
measured according to ASTM E-112.
[0060] Testing was also conducted to determine correlation between grain size and dielectric
breakdown strength of one embodiment of the inventive material (09-B-29) over a range
of firing temperatures. The specimens used for this testing were disks with thickness
of about 3.5 mm, while the dielectric testing previously described was performed on
insulators with wall thickness of 2.0 mm. The dielectric breakdown strength was measured
according to ASTM D-149 and particle size was measured according to ASTM E-112.
[0061] The ceramic material provides a higher thermal conductivity compared to prior art
ceramic materials used for spark plug insulators. One embodiment of the inventive
ceramic material (08-B-10) has a thermal conductivity at room temperature of about
35 W/mK, whereas prior art ceramic materials typically have a thermal conductivity
at room temperature of about 24 W/mK. The thermal conductivity is measured after sintering
the ceramic material and can be measured by the laser flash method (ASTM E 1461).
[0062] Obviously, many modifications and variations of the present invention are possible
in light of the above teachings and may be practiced otherwise than as specifically
described while within the scope of the invention.
1. A ceramic material for an insulator (22) of a spark plug (20) comprising, in weight
percent (wt%) of said ceramic material, aluminum oxide (Al2O3) in an amount of 98.00 wt% to 99.50 wt%; wherein said Al2O3 is formed of particles having a D50 median particle size by volume of 1.2 µm to 1.8
µm and a D90 particle size by volume of 2.5 µm to 6.0 µm;
at least one oxide of a Group 2 alkaline earth metal (Group 2 oxide) in an amount
of 0.16 wt% to 0.70 wt%, wherein said Group 2 oxides are selected from the group consisting
of calcium oxide (CaO), magnesium oxide (MgO), beryllium oxide (BeO), strontium oxide
(SrO), barium oxide (BaO), and radium oxide (RaO); at least one oxide of a Group 4
transition metal (Group 4 oxide) in an amount of 0.01 wt% to 0.16 wt%, wherein said
Group 4 oxides are selected from the group consisting of: zirconium oxide (ZrO2) titanium dioxide (TiO2), hafnium oxide (HfO2), and rutherfordium oxide (RfO2); and silicon dioxide (SiO2) in an amount of 0.25 wt% to 0.75 wt%.
2. A ceramic material as set forth in claim 1 wherein said Al2O3 is formed of particles having a specific surface area of 2.0 m2/g to 5.0 m2/g.
3. A ceramic material as set forth in claim 1 including MgO in an amount of 0.01 wt%
to 0.15 wt % and CaO in an amount of 0.15 wt% to 0.55 wt%.
4. A ceramic material as set forth in claim 1 including ZrO2 and TiO2 in an amount of 0.07 wt% to 0.10 wt%.
5. A ceramic material as set forth in claim 1 including ZrO2 in an amount of 0.01 wt% to 0.15 wt% and TiO2 in an amount of up to 0.01 wt%.
6. A ceramic material as set forth in claim 1 including at least one oxide of a Group
1 alkali metal (Group 1 oxide) in an amount less than 0.0060 wt%, and wherein said
at least one Group 1 oxide includes at least one of potassium oxide (K2O), sodium oxide (Na2O), lithium oxide (Li2O), rubidium oxide (Rb2O), cesium oxide (Cs2O), and francium oxide (Fr2O).
7. A ceramic material as set forth in claim 6, including K2O and Na2O in an amount less than 0.0060 wt%.
8. A ceramic material as set forth in claim 1 including a glass phase in an amount of
0.50 wt% to 2.0 wt%, and wherein said glass phase includes at least a portion of said
Al2O3, said Group 2 oxides, and said SiO2.
9. A ceramic material as set forth in claim 8 wherein said glass phase includes, in weight
percent of said glass phase, said Al2O3 in an amount of 5.0 wt% to 50.0 wt%, said SiO2 in an amount of 27.0 wt% to 50.0 wt%, and wherein said Group 2 oxides include CaO
in an amount 15.0 wt% to 24.0 wt% and MgO in an amount of 0.5 wt% to 7.7 wt%.
10. A ceramic material as set forth in claim 1 including secondary crystals comprising
at least a portion of said Al2O3, said Group 2 oxides, and said SiO2, and wherein said secondary crystals further include at least one of calcium hexa-aluminate
(CaAl12O19) spinel (MgAl2O4), anorthite (CaAl2Si2O8), and mullite (Al6Si2O13).
11. A ceramic material as set forth in claim 1 including said Al2O3 in an amount of 98.85 wt%, said Group 2 oxides in an amount of 0.46 wt%, and said
SiO2 in an amount of 0.60 wt%.
12. A ceramic material as set forth in claim 1 wherein said Group 2 oxides include CaO
and MgO and including said Al2O3 in an amount of 98.85 wt%, said CaO in an amount of 0.39 wt%, said MgO in an amount
of 0.073 wt%, said SiO2 in an amount of 0.60 wt%, TiO2 in an amount of 0.004 wt%, ZrO2 in an amount of 0.08 wt%, K2O in an amount of 0.003 wt%, Na2O in an amount of 0.0007 wt%, and P2O5 in an amount of 0.0027 wt%.
13. A ceramic material as set forth in claim 1 wherein said Group 2 oxides include CaO
and MgO and including said Al2O3 in an amount of 98.80 wt%, said CaO in an amount of 0.46 wt%, said MgO in an amount
of 0.037 wt%, said SiO2 in an amount of 0.62 wt%, TiO2 in an amount of 0.005 wt%, ZrO2 in an amount of 0.08 wt%, K2O in an amount of 0.004 wt%, Na2O in an amount of 0.0008 wt%, and P2O5 in an amount of 0.0031 wt%.
14. A spark plug (20) including an insulator (22) formed of the ceramic material of claim
1.
15. A method of fabricating a spark plug (20) including an insulator (22) formed of a
ceramic material comprising the steps of:
providing ceramic particles including, in weight percent wt% of the ceramic material,
aluminum oxide (Al2O3) having a D50 median particle size of 1.2 µm to 1.8 µm and a D90 particle size by
volume of 2.5 µm to 6.0 µm in an amount of 98.00 wt% to 99.50 wt%, at least one oxide
of a Group 2 alkali earth metal (Group 2 oxide) in an amount of 0.16 wt% to 0.70 wt%,
wherein the Group 2 oxides are selected from the group consisting of: calcium oxide
(CaO), magnesium oxide (MgO), beryllium oxide (BeO), strontium oxide (SrO), barium
oxide (BaO), and radium oxide (RaO); at least one oxide of a Group 4 transition metal
(Group 4 oxide) in an amount of 0.01 wt% to 0.16 wt%, wherein said Group 4 oxides
are selected from the group consisting of: zirconium oxide (ZrO2), titanium dioxide (TiO2), hafnium oxide (HfO2), and rutherfordium oxide (RfO2); and silicon dioxide (SiO2) in an amount of 0.25 wt% to 0.75 wt%;
pressing the ceramic particles;
sintering the ceramic particles; and
forming the ceramic particles to a predetermined shape.
1. Keramischer Werkstoff für einen Isolator (22) einer Zündkerze (20), bestehend in Gewichtsprozent
(Gew.-%) des keramischen Werkstoffs aus Aluminiumoxid (Al2O3) in einem Anteil von 98,00 bis 99,50 Gew.-%, wobei das Al2O3 aus Partikeln gebildet ist, die eine mittlere Partikelgröße D50 volumetrischen Durchmessers
von 1,2 µm bis 1,8 µm und eine Partikelgröße D90 volumetrischen Durchmessers von 2,5
µm bis 6,0 µm besitzen;
mindestens einem Oxid eines Erdalkalimetalls der II. Gruppe (Oxid der II. Gruppe)
in einem Anteil von 0,16 bis 0,70 Gew.-%, wobei die Oxide der II. Gruppe aus der aus
Kalziumoxid (CaO), Magnesiumoxid (MgO), Berylliumoxid (BeO), Strontiumoxid (SrO),
Bariumoxid (BaO) und Radiumoxid (RaO) bestehenden Gruppe ausgewählt sind; mindestens
einem Oxid eines Übergangsmetalls der IV. Gruppe (Oxid der IV. Gruppe) in einem Anteil
von 0,01 bis 0,16 Gew.-%, wobei die Oxide der IV. Gruppe aus der aus Zirconiumoxid
(ZrO2), Titandioxid (TiO2), Hafniumoxid (HfO2) und Rutherfordiumoxid (RfO2) bestehenden Gruppe ausgewählt sind; sowie Siliziumdioxid (SiO2) in einem Anteil von 0,25 bis 0,75 Gew.-%.
2. Keramischer Werkstoff nach Anspruch 1, bei dem das Al2O3 aus Partikeln gebildet ist, die eine spezifische Oberfläche von 2,0 bis 5,0 m2/g besitzen.
3. Keramischer Werkstoff nach Anspruch 1 mit MgO in einem Anteil von 0,01 bis 0,15 Gew.-%
und CaO in einem Anteil von 0,15 bis 0,55 Gew.-%.
4. Keramischer Werkstoff nach Anspruch 1 mit ZrO2 und TiO2 in einem Anteil von 0,07 bis 0,10 Gew.-%.
5. Keramischer Werkstoff nach Anspruch 1 mit ZrO2 in einem Anteil von 0,01 bis 0,15 Gew.-% und TiO2 in einem Anteil von bis zu 0,01 Gew.-%.
6. Keramischer Werkstoff nach Anspruch 1 mit mindestens einem Oxid eines Alkalimetalls
der I. Gruppe (Oxid der I. Gruppe) in einem Anteil von weniger als 0,0060 Gew.-%,
und bei dem das mindestens eine Oxid der I. Gruppe Kaliumoxid (K2O), Natriumoxid (Na2O), Lithiumoxid (Li2O), Rubidiumoxid (Rb2O), Zäsiumoxid (Cs2O) und/oder Franciumoxid (Fr2O) enthält.
7. Keramischer Werkstoff nach Anspruch 6 mit K2O und Na2O in einem Anteil von weniger als 0,0060 Gew.-%.
8. Keramischer Werkstoff nach Anspruch 1 mit einer Glasphase in einem Anteil von 0,50
bis 2,0 Gew.-%, und bei dem die Glasphase mindestens einen Teil des Al2O3, der Oxide der II. Gruppe und des SiO2 enthält.
9. Keramischer Werkstoff nach Anspruch 8, bei dem die Glasphase in Gewichtsprozent der
Glasphase das Al2O3 in einem Anteil von 5,0 bis 50,0 Gew.-%, das Si2O in einem Anteil von 27,0 bis 50,0 Gew.-% enthält, und bei dem die Oxide der II.
Gruppe CaO in einem Anteil von 15,0 bis 24,0 Gew.-% und MgO in einem Anteil von 0,5
bis 7,7 Gew.-% enthalten.
10. Keramischer Werkstoff nach Anspruch 1 mit Sekundär-Kristallen, die mindestens einen
Teil des Al2O3, der Oxide der II. Gruppe und des Si2O enthalten, und bei dem die Sekundär-Kristalle des Weiteren Kalziumhexaaluminat (CaAl12O19), Spinell (MgAl2O4), Anorthit (CaAl2Si2O8) und/oder Mullit (Al6Si2O13) enthalten.
11. Keramischer Werkstoff nach Anspruch 1 mit dem Al2O3 in einem Anteil von 98,85 Gew.-%, den Oxiden der II. Gruppe in einem Anteil von 0,46
Gew.-% und dem SiO2 in einem Anteil von 0,60 Gew.-%.
12. Keramischer Werkstoff nach Anspruch 1, bei dem die Oxide der II. Gruppe CaO und MgO
enthalten und das Al2O3 in einem Anteil von 98,85 Gew.-%, das CaO in einem Anteil von 0,39 Gew.-%, das MgO
in einem Anteil von 0,073 Gew.-%, das SiO2 in einem Anteil von 0,60 Gew.-%, TiO2 in einem Anteil von 0,004 Gew.-%, ZrO2 in einem Anteil von 0,08 Gew.-%, K2O in einem Anteil von 0,003 Gew.-%, Na2O in einem Anteil von 0,0007 Gew.-% und P2O5 in einem Anteil von 0,0027 Gew.-% einschließen.
13. Keramischer Werkstoff nach Anspruch 1, bei dem die Oxide der II. Gruppe CaO und MgO
umfassen und das Al2O3 in einem Anteil von 98,80 Gew.-%, das CaO in einem Anteil von 0,46 Gew.-%, das MgO
in einem Anteil von 0,037 Gew.-%, das SiO2 in einem Anteil von 0,62 Gew.-%, TiO2 in einem Anteil von 0,005 Gew.-%, ZrO2 in einem Anteil von 0,08 Gew.-%, K2O in einem Anteil von 0,004 Gew.-%, Na2O in einem Anteil von 0,0008 Gew.-% und P2O5 in einem Anteil von 0,0031 Gew.-% einschließen.
14. Zündkerze (20) mit einem Isolator (22), der aus dem keramischen Werkstoff nach Anspruch
1 gebildet ist.
15. Verfahren zum Herstellen einer Zündkerze (20) mit einem Isolator (22), der aus einem
keramischen Werkstoff gebildet ist, mit den Schritten:
Bereitstellen von Keramikpartikeln, die in Gewichtsprozent (Gew.-%) des keramischen
Werkstoffs Aluminiumoxid (Al2O3) mit einer mittleren Partikelgröße D50 volumetrischen Durchmessers von 1,2 µm bis
1,8 µm und einer Partikelgröße D90 volumetrischen Durchmessers von 2,5 µm bis 6,0
µm und in einem Anteil von 98,00 bis 99,50 Gew.-%, mindestens ein Oxid eines Erdalkalimetalls
der II. Gruppe (Oxid der II. Gruppe) in einem Anteil von 0,16 bis 0,70 Gew.-%, wobei
die Oxide der II. Gruppe aus der aus: Kalziumoxid (CaO), Magnesiumoxid (MgO), Berylliumoxid
(BeO), Strontiumoxid (SrO), Bariumoxid (BaO) und Radiumoxid (RaO) bestehenden Gruppe
ausgewählt sind; mindestens ein Oxid eines Übergangsmetalls der IV. Gruppe (Oxid der
IV. Gruppe) in einem Anteil von 0,01 bis 0,16 Gew.-%, wobei die Oxide der IV. Gruppe
aus der aus: Zirconiumoxid (ZrO2), Titandioxid (TiO2), Hafniumoxid (HfO2) und Rutherfordiumoxid (RfO2) bestehenden Gruppe ausgewählt sind; und Siliziumdioxid (SiO2) in einem Anteil von 0,25 bis 0,75 Gew.-% enthalten;
Pressen der Keramikpartikel;
Sintern der Keramikpartikel; und
Formen der Keramikpartikel zu einer vorgegebenen Form.
1. Matériau céramique pour isolateur (22) d'une bougie d'allumage (20) comprenant, en
pourcent en poids (% en poids) dudit matériau céramique, de l'oxyde d'aluminium (Al2O3) en une quantité de 98,00 % en poids à 99,50 % en poids, où ledit Al2O3 est formé de particules ayant une taille de particule médiane D50 en volume de 1,2
µm à 1,8 µm et une taille de particule D90 en volume de 2,5 µm à 6,0 µm ;
au moins un oxyde d'un métal alcalino-terreux du groupe 2 (oxyde du groupe 2) en une
quantité de 0,16 % en poids à 0,70 % en poids, où lesdits oxydes du groupe 2 sont
choisis dans le groupe consistant en l'oxyde de calcium (CaO), l'oxyde de magnésium
(MgO), l'oxyde de béryllium (BeO), l'oxyde de strontium (SrO), l'oxyde de baryum (BaO)
et l'oxyde de radium (RaO) ; au moins un oxyde d'un métal de transition du groupe
4 (oxyde du groupe 4) en une quantité de 0,01 % en poids à 0,16 % en poids, où lesdits
oxydes du groupe 4 sont choisis dans le groupe consistant en : l'oxyde de zirconium
(ZrO2), le dioxyde de titane (TiO2), l'oxyde de hafnium (HfO2) et l'oxyde de rutherfordium (RfO2); et le dioxyde de silicium (SiO2) en une quantité de 0,25 % en poids à 0,75 % en poids.
2. Matériau céramique selon la revendication 1 où ledit Al2O3 est formé de particules ayant une surface spécifique de 2,0 m2/g à 5,0 m2/g.
3. Matériau céramique selon la revendication 1 incluant MgO en une quantité de 0,01 %
en poids à 0,15 % en poids et CaO en une quantité de 0,15 % en poids à 0,55 % en poids.
4. Matériau céramique selon la revendication 1 incluant ZrO2 et TiO2 en une quantité de 0,07 % en poids à 0,10 % en poids.
5. Matériau céramique selon la revendication 1 incluant ZrO2 en une quantité de 0,01 % en poids à 0,15 % en poids et TiO2 en une quantité de jusqu'à 0,01 % en poids.
6. Matériau céramique selon la revendication 1 incluant au moins un oxyde d'un métal
alcalin du groupe 1 (oxyde du groupe 1) en une quantité inférieure à 0,0060 % en poids,
et où ledit au moins un oxyde du groupe 1 inclut au moins l'un de l'oxyde de potassium
(K2O), l'oxyde de sodium (Na2O), l'oxyde de lithium (Li2O), l'oxyde de rubidium (Rb2O), l'oxyde de césium (Cs2O) et l'oxyde de francium (Fr2O).
7. Matériau céramique selon la revendication 6, incluant K2O et Na2O en une quantité inférieure à 0,0060 % en poids.
8. Matériau céramique selon la revendication 1 incluant une phase vitreuse en une quantité
de 0,50 % en poids à 2,0 % en poids, et où ladite phase vitreuse inclut au moins une
partie dudit Al2O3, desdits oxydes du groupe 2 et dudit SiO2.
9. Matériau céramique selon la revendication 8 où ladite phase vitreuse inclut, en pourcent
en poids de ladite phase vitreuse, ledit Al2O3 en une quantité de 5,0 % en poids à 50,0 % en poids, ledit SiO2 en une quantité de 27,0 % en poids à 50,0 % en poids, et où lesdits oxydes du groupe
2 incluent CaO en une quantité de 15,0 % en poids à 24,0 % en poids et MgO en une
quantité de 0,5 % en poids à 7,7 % en poids.
10. Matériau céramique selon la revendication 1 incluant des cristaux secondaires comprenant
au moins une partie dudit Al2O3, desdits oxydes du groupe 2 et dudit SiO2, et où lesdits cristaux secondaires incluent en outre au moins l'un de l'hexa-aluminate
de calcium (CaAl12O19), le spinelle (MgAl2O4), l'anorthite (CaAl2Si2O8) et la mullite (Al6Si2O13).
11. Matériau céramique selon la revendication 1 incluant ledit Al2O3 en une quantité de 98,85 % en poids, lesdits oxydes du groupe 2 en une quantité de
0,46 % en poids, et ledit SiO2 en une quantité de 0,60 % en poids.
12. Matériau céramique selon la revendication 1 où lesdits oxydes du groupe 2 incluent
CaO et MgO et incluant ledit Al2O3 en une quantité de 98,85 % en poids, ledit CaO en une quantité de 0,39 % en poids,
ledit MgO en une quantité de 0,073 % en poids, ledit SiO2 en une quantité de 0,60 % en poids, TiO2 en une quantité de 0,004 % en poids, ZrO2 en une quantité de 0,08 % en poids, K2O en une quantité de 0,003 % en poids, Na2O en une quantité de 0,0007 % en poids, et P2O5 en une quantité de 0,0027 % en poids.
13. Matériau céramique selon la revendication 1 où lesdits oxydes du groupe 2 incluent
CaO et MgO et incluant ledit Al2O3 en une quantité de 98,80 % en poids, ledit CaO en une quantité de 0,46 % en poids,
ledit MgO en une quantité de 0,037 % en poids, ledit SiO2 en une quantité de 0,62 % en poids, TiO2 en une quantité de 0,005 % en poids, ZrO2 en une quantité de 0,08 % en poids, K2O en une quantité de 0,004 % en poids, Na2O en une quantité de 0,0008 % en poids, et P2O5 en une quantité de 0,0031 % en poids.
14. Bougie d'allumage (20) incluant un isolateur (22) formé du matériau céramique selon
la revendication 1.
15. Procédé de fabrication d'une bougie d'allumage (20) incluant un isolateur (22) formé
d'un matériau céramique comprenant les étapes de :
fourniture de particules céramiques incluant, en pourcent en poids % en poids du matériau
céramique, de l'oxyde d'aluminium (Al2O3) ayant une taille de particule médiane D50 de 1,2 µm à 1,8 µm et une taille de particule
D90 en volume de 2,5 µm à 6,0 µm en une quantité de 98,00 % en poids à 99,50 % en
poids, au moins un oxyde d'un métal alcalino-terreux du groupe 2 (oxyde du groupe
2) en une quantité de 0,16 % en poids à 0,70 % en poids, où les oxydes du groupe 2
sont choisis dans le groupe consistant en l'oxyde de calcium (CaO), l'oxyde de magnésium
(MgO), l'oxyde de beryllium (BeO), l'oxyde de strontium (SrO), l'oxyde de baryum (BaO)
et l'oxyde de radium (RaO) ; au moins un oxyde d'un métal de transition du groupe
4 (oxyde du groupe 4) en une quantité de 0,01 % en poids à 0,16 % en poids, où lesdits
oxydes du groupe 4 sont choisis dans le groupe consistant en : l'oxyde de zirconium
(ZrO2), le dioxyde de titane (TiO2), l'oxyde de hafnium (HfO2) et l'oxyde de rutherfordium (RfO2) ; et le dioxyde de silicium (SiO2) en une quantité de 0,25 % en poids à 0,75 % en poids ;
compression des particules céramiques ;
frittage des particules céramiques ; et
mise en forme des particules céramiques en une forme prédéterminée.